WO2012118713A2 - Process for patterning materials in thin-film devices - Google Patents
Process for patterning materials in thin-film devices Download PDFInfo
- Publication number
- WO2012118713A2 WO2012118713A2 PCT/US2012/026565 US2012026565W WO2012118713A2 WO 2012118713 A2 WO2012118713 A2 WO 2012118713A2 US 2012026565 W US2012026565 W US 2012026565W WO 2012118713 A2 WO2012118713 A2 WO 2012118713A2
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- WO
- WIPO (PCT)
- Prior art keywords
- layer
- photo
- patternable
- fluorinated
- substrate
- Prior art date
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
- H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
- H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
- H10K71/221—Changing the shape of the active layer in the devices, e.g. patterning by lift-off techniques
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/50—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor for integrated circuit devices, e.g. power bus, number of leads
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/464—Lateral top-gate IGFETs comprising only a single gate
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/80—Constructional details
- H10K10/82—Electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
- H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
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- G03F7/203—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure comprising an imagewise exposure to electromagnetic radiation or corpuscular radiation
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
- G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
Definitions
- the present disclosure provides a method for patterning active layers in devices to permit two, distinct, patterns to be formed in two or more different active layers following a single photolithographic step. This process can be employed to form multilayer, patterned organic or inorganic devices.
- OLEDs Organic Light Emitting Diodes
- OLED technology particularly OLED display technology
- This slow adoption rate stems at least partially from the high cost of patterning these materials to form a practical display device.
- Various approaches to patterning organic materials to form full color OLED displays have been attempted. Patterning of different colors of material by vapor deposition of organic materials through shadowmasks has proven to be effective. However these shadowmasks limit the resolution of the displays, the size of the substrate that can be successfully coated, and increase the tact time.
- Other approaches, such as the use of laser deposition to pattern color emitters has been demonstrated but this technology often produces displays with low yields and often results in significant residual waste.
- Solution printing of different colored organic emitters has also been discussed but these processes typically result in emitters with significantly lower emission efficiency as compared to emitters deposited by vapor deposition. This lower efficiency is due to increased contact resistance and the fact that polymeric materials, that are often used, often have a lower luminescent efficiency and lifetime than small molecule materials and the use of solution deposition limits the number of layers that can be deposited on one another to manage the movement of carriers through the organic layer.
- Other approaches to forming multicolor OLED devices have also been attempted, including the use of white emitters together with patterned color filters. However, these approaches also reduce the effective efficiency of the emitters within the OLED display.
- Other organic devices, including oTFTs suffer from similar patterning issues.
- OLED display structures including one or blanket-coated emitting layers.
- Miller et al in US Patent 7, 142, 179, entitled “OLED display device”, issued on November 26, 2006 and Cok et al in US Patent 7,250,722, entitled “OLED device”, issued on July 31, 2007, each discuss a structure having a first OLED constructed between a first and a second patterned electrode and a second OLED constructed between the second patterned electrode and a blanket-coated electrode.
- the first OLED must be patterned to permit the second pattern electrode to be connected to the substrate. Further the second electrode must be patterned after it is deposited over the OLED.
- These structures produce higher efficiency light output without patterning at least one of the layers of organic materials.
- these structures require the patterning of very small structures through an organic layer to form a via hole through the organic material, as well as the patterning of a conductive layer over an organic layer.
- Robust processes for providing these vias and forming the electrode pattern over an organic layer in a high speed manufacturing environment are not known in the art and therefore these device structures have not been successfully manufactured.
- Similar structures are also desirable for the formation of multi-layer photovoltaic and other organic devices.
- inorganic electronic devices it is known to apply photolithographic techniques to pattern multiple thin film layers of inorganic semiconductors and inorganic electrically conductive layers with high resolution over large substrates for forming arrays of electrical components.
- the photolithographic materials and solvents applied to form these devices are known to dissolve organic materials. Therefore, it is not possible to apply the photolithographic materials and solvents that are known to be used to manufacture inorganic solid state circuits to pattern layers of organic material, especially layers that include active
- Taussig et al in United States Patent 7,202, 179 entitled “Method of forming at least one thin film device", issued on April 10, 2007 discusses a method in which a 3D template is used to emboss a 3D structure over the layers of a device and the 3D structure and the underlying layers are etched to provide the final structure.
- This method permits different patterns to be formed in different layers of a device as the result of using a single imprint lithographic step so that alignment of multiple lithographic steps is not required, permitting this method to be applied to form devices on substrates that are not stable, for example, plastics which expand or contract during manufacturing.
- the method provided is only useful with inorganic structures as the method applies materials and methods that are not compatible with organic semiconductor materials. Further, the method applies techniques that are not currently used in high volume manufacturing and requires strict process control to permit the patterning steps to achieve the desired result.
- the present disclosure provides a method for forming a device that includes providing a substrate; depositing a single fluorinated photo-patternable layer over the substrate; forming a first and a second active layer over the substrate; and applying the photo-patternable layer to form a first pattern within the first active layer and a second, different pattern within the second active layer.
- Particular examples disclosed in the present disclosure can be employed to form thin film electronics devices, including OLED devices and TFTs with a reduced number of photolithographic steps.
- aspects of the present disclosure provide the advantage of permitting multiple layers within a device to be uniquely patterned through the deposition, exposure, and development of a single photosensitive material layer.
- This process can be applied in either organic or inorganic devices and enables the patterning of multiple layers, some of which are organic layers, within a device.
- this method permits multilayer organic devices to be formed without removing the devices from inert environments during manufacture, permitting the formation of high quality organic device structures that were not previously possible in high volume manufacturing environments. Because many of the layers of a device can be patterned from a single exposure, aspects of the present disclosure also permit the manufacturing of thin-film devices on unstable, flexible substrates.
- this method has all of the advantages of traditional photolithographic methods, including providing a very high resolution (e.g., resolution on the order of a micron) in a highly parallel and therefore rapid process. Additionally this method permits devices to be performed with fewer photolithographic steps, significantly reducing total tact time, eliminating the need to deposit and develop multiple layers of photosensitive material during manufacture and therefore significantly reduces the cost of manufacture.
- FIG. 1 flow diagram depicting the steps of an example an illustrative method of present invention
- FIG. 2 flow diagram depicting the detailed steps of an embodiment of the present invention
- FIG. 3 process diagram illustrating the steps of an example of the method of the present invention for forming an OLED display
- FIG. 4 process diagram illustrating the steps of an example of the method of the present invention for forming an array of TFTs
- FIG. 5 flow diagram illustrating the steps of an example of the method of the present invention for forming an array of TFTs.
- aspects of the present invention provide a method for forming a thin film device as shown in FIG. 1.
- Thin film devices in certain instances of the present disclosure include devices having organic as well as inorganic thin film layers.
- aspects of the present disclosure provide a method for forming a device that includes providing 2 a substrate, depositing 4 a single fluorinated photo-patternable layer over the substrate, forming 6, 8 a first and a second active layer over the substrate, and applying 10 the photo-patternable layer to form a first pattern within the first active layer and a second, different pattern within the second active layer.
- the photo-patternable layer can be exposed to radiation to create three unique, non-overlapping patterns of exposed material, depositing two material layers that are active or functional within the final device and applying the photo-patternable layer to impart different patterns into each of the two active material layers.
- These different patterns are typically imparted to the two active material layers by exposing the photo-patternable layer to a first fluorinated solvent to develop a first pattern and at least a second fluorinated solvent to develop at least a second pattern within the photo-patternable layer .
- a pattern in the fluorinated photo-patternable layer is typically transferred to an active material layer through liftoff or etching. When applying liftoff, the process steps can be ordered as shown in FIG. 1.
- the fluorinated photo-patternable layer can be deposited 4 after the forming 6, 8 the first and the second active layers.
- the photo-patternable layer can include a highly fluorinated material layer and the solvents can include highly fluorinated solvents.
- Some embodiments of the method of the present invention rely upon two separate experimental observations that have been made by the inventors. First the inventors have observed that when a single fluorinated photo-patternable layer is deposited on a substrate and different portions of the fluorinated photo-patternable layer are exposed to different amounts of radiation, the portions having a lower exposure can be removed by a larger number of fluorinated solvents than the portions having a higher exposure. Therefore, by controlling the exposure and selecting the appropriate fluorinated solvents, different portions of the fluorinated photo-patternable layer can be removed at different times, permitting additional process steps to be completed between the times that these different portions are removed.
- the inventors have observed that it is possible to form a bi-layer of a fluorinated photo-patternable layer and a traditional non-fluorinated photo- patternable layer wherein the two layers perform independently of one another without chemical interaction and in such a way that the exposure of the two layers can be differentially controlled. Further, when the non-fluorinated photo- patternable layer is removed over portions of the fluorinated photo-patternable layer, the exposed portions of the fluorinated photo-patternable layer can be lifted off much more quickly and easily than the portions of the fluorinated photo-patternable layer underlying the non-fluorinated photo-patternable layer.
- the use of the bi- layer can provide additional differentiation in solvent sensitivity and provide the ability to form another region that can be removed at another time.
- the use of this bi-layer has another advantage when employing liftoff as removal of the portion of the fluorinated photo-patternable layer that is exposed by removing a portion of the non-fluorinated photo-patternable layer can result in a significant undercut profile for the remaining portions of the fluorinated photo-patternable layer.
- an "organic device” is a device that contains an active layer that includes organic molecules (i.e., molecules containing hydrogen and carbon atoms). In certain embodiments, these organic molecules are organic semiconductors, such as Alq or organic conductors such as Pentacene. Conversely, an “inorganic device” is a device that contains no active layers which include organic molecules.
- An “active layer” is a layer that is functional within the device that is being constructed. Often in thin film electronic devices, such as the ones targeted by certain aspects of the present invention, the active layers can include a semiconductor or a conductor but can also include an insulator.
- An active layer can be a single homogenous layer but alternately can include multiple thin film layers that together form a functional layer within the device.
- an active layer may include each of the organic layers within the diode, often including a hole transport or an electron transport layer.
- One of these layers or a separate, intermediate thin film layer can further provide light emission.
- the handling of organic materials can require special care. The performance of some organic semiconductors can be significantly degraded through exposure to air or moisture. Further most organic materials are highly soluble in the non-fluorinated solvents applied in traditional photolithography and therefore it is not desirable to apply these solvents to devices after the deposition of organic materials. However, the organic materials are not soluble in typical highly fluorinated solvents and therefore these solvents can be applied after organic materials are deposited in a device.
- Certain embodiments of the method of the present invention are applicable to "thin film” devices. These devices typically include layers that that are less than 200 nm thick and often are less than 50 nm thick. Layers in thin film devices are often deposited using techniques such as evaporation, sputtering or solution coating. These devices are typically formed on a “substrate” which is a support for providing structural integrity to prevent the thin-film layers in the device from coming apart.
- substrate refers to any support on which thin film layers can be coated to provide structural integrity.
- Substrates known in the art include rigid substrates, such as those typically formed from glass, and flexible substrates, such as typically formed from stainless steel foil or plastic.
- the substrate can also provide a portion of an environmental barrier to protect any organic material from moisture or oxygen, but this is not required.
- the substrate can be opaque, transparent or semitransparent.
- the substrate can further include one or more layers, such as metal bus lines or inorganic semiconductor materials for conducting electricity to the device.
- the substrate can include nonconductive layers of organic material to perform functions, such as insulating the active layers from the substrate or conductive elements on the substrate. Nonconductive organic layers can also be included as part of the substrate when these layers are provided to smooth the surface of the substrate to permit a uniform layer of the thin film layers to be formed.
- etch refers to a process in which the remaining portion or portions of a photo-patternable layer is used to protect the underlying regions of an active layer from exposure to a removal process.
- remaining portions of the photo-patternable layer can protect portions of an active layer from a plasma stream which vaporizes the unprotected portions of an active organic layer, removing them from the substrate.
- Various chemistries and etching processes can be applied to remove different materials as known in the art and the etching methods can be selected or tuned to be selective having a large effect on a particular first material while having little or no effect on a different, second material.
- liftoff refers to a process in which the active layer is deposited over a portion of the photo-patternable layer and the substrate is exposed to a solvent that removes a portion of the photo-patternable layer, thus removing the overlying portion of the active layer.
- the term “pattern” within the present disclosure refers to a spatial arrangement within the photo-patternable layer that differs in physical or chemical properties from other portions of the photo- patternable layer.
- the term “pattern” refers specifically to a physical pattern that is created by removing a significant portion of the active layer in a specific pattern, creating a layer of varying thickness and ideally a layer which is present in some physical locations and not present within other physical locations.
- the term "pattern” refers to a spatial arrangement that is created by substantially removing a first portion of the active layer over some areas of the substrate while leaving a second portion of the active layer in substantially in tact over other areas of the substrate.
- exposure is applied in two different contexts within this document, specifically exposure to a solvent or exposure to radiation. Exposure to a solvent typically involves immersion in a solvent, simultaneously or uniformly coating the entire substrate in the solvent. However, the term “expose” when applied to radiation applies to a process in which the dose or exposure degree of radiation is controlled and typically varied across the substrate so that some regions receive a larger dose than others.
- This last method can be combined with laser patterning on a roll-to-roll format, when forming repeated elements such as backplane transistors.
- a laser can be imaged through a holographic film to create a pattern having multiple exposure areas on the substrate while the laser is imaged in a fixed position with respect to the substrate and can image one or more elements (e.g., TFTs or OLED pixels), the laser can then moved to a different location on the substrate and used to image another element or group of elements.
- the area over the via holes and around each element would be defined at this time.
- Electrodes refers to layer or a combination of multiple thin film layers which functionally provide a single conductive layer capable of creating an electrical field within the thin film layers of the device.
- An electrode can be transparent, semi-transparent, or opaque. However, at least one of a first or second electrode in the OLED devices of the present disclosure can be transparent or semi- transparent. Often one of the first or second electrodes within devices in certain embodiments of the present invention can be opaque and reflective. Typical electrodes useful in certain embodiments of the present invention can have a thickness of between 10 and 300 nm. Electrodes can be formed from organic or inorganic materials capable of conducting electricity to create an electric field within the thin film layers of the devices in certain embodiments of the present invention.
- Typical inorganic materials useful in forming an electrode can include metals such as silver, gold, platinum, copper, molybdenum and aluminum; as well as certain doped metal oxides, such as indium tin oxide or indium zinc oxide. Electrodes can be formed using multiple methods including printing or sputtering. However, it is desirable in certain embodiments to deposit the inorganic materials to form an electrode using evaporation or other methods that provide line of sight deposition. Organic materials useful in forming an electrode include highly ordered polymers, such as PEDOT/PSS. Electrodes can be formed using numerous methods, including printing methods. However, to increase deposition speed and decrease process time, it is preferred that the material used to form electrodes, especially the material used to form the second electrode be deposited using blanket-coating methods to form a continuous film over the substrate.
- patterned electrode refers specifically to electrodes that are segmented across the substrate such that each segment of the electrode is shared by one or more electrical component or light-emitting elements but all electrical components or light-emitting elements on the substrate do not share the same segment of the electrode. That is, the flow of current through any two segments of the electrode can be independently controlled to independently control the flow of current through the electrical component or light-emitting element that is in contact with each segment.
- the fluorinated photoresist material which is applied to form the "fluorinated photo-patternable layer” can be a resorcinarene, a copolymer of perfluorodecyl methacrylate and 2-nitrobenzyl methacrylate, derivatives thereof or other polymer photoresist or molecular glass photoresist having sufficient content to permit the photoresist to be dissolved in a fluorinated solvent such as a solvent formed from a hydrofluorether.
- a fluorinated solvent such as a solvent formed from a hydrofluorether.
- This fluorinated photoresist can be solubulized in a hydrofluroether such as methyl nonafluorobutyl ether and then coated onto a substrate. The solvent can then be evaporated to form a photo-patternable layer.
- This solvent can also include a photo-acid generator, for example N-hydroxynaphthalamide
- this photoresist can be a material composed of a copolymer of lH, lH,2H,2H-perfluorodecyl methacrylate (FDMA) and tert-butyl methacrylate (TBMA).
- FDMA lH, lH,2H,2H-perfluorodecyl methacrylate
- TBMA tert-butyl methacrylate
- a 25 ml round bottom flask equipped with a stir bar was filled with 1.4g of FDMA, 0.6g of TBMA, 0.01 g of AIBN and 2 ml of trifluorotoluene as a solvent. After polymerization, the reaction mixture was poured into hexane to precipitate the polymer and then filtered and dried under vacuum. The molecular weight of the copolymer was determined to be 30400 by size-exclusion chromatography and the molar composition of
- FDMA:TBMA was found to be 35 mol%:65 mol% using 1H NMR (Varian Inova- 400 spectrometer) analysis with CDCI3-CFCI3 (v/v - 1 :3.5) as a solvent.
- FDMA component of the resist is responsible for the solubility of the copolymer in fluorinated solvents whereas the TBMA groups in the unexposed regions make the copolymer less polar in the butyl-protected state.
- these protecting groups undergo a chemically amplified deprotection reaction.
- the resulting polar methacrylic acid (MAA) units decrease copolymer solubility in fluorinated solvents.
- the exposed pattern can be treated with a solubilizing agent, for example a silazine such as HMDS. This treatment re-protects the P(FDMA-coMAA) film with siloxane groups and makes it soluble within selected fluorinated solvents to facilitate its removal for liftoff.
- the resorcinarene and FDMA:TBMA copolymer are chemically amplified resists.
- this attribute of these resists can be particularly desirable since they enable the expose photoresist step to be performed through the application of a relatively low energy UV light exposure (typically under 100 mJ/cm 2 ).
- This is particularly important in devices employing organic compounds which are deposited before the fluorinated photo-patternable layer is deposited 4 since many organic materials useful in forming the one or more organic layers can decompose in the presence of UV light and therefore, reduction of the energy during this step permits the photoresist to be exposed without causing significant damage to the underlying one or more organic layers.
- due to the high fluorine content in each of these photoresists they are both hydrophobic and oleophobic.
- Fluorinated solvents appropriate for use of the first, second or third fluorinated solvent is perfluorinated or highly fluorinated liquids, which are typically immiscible with organic solvents and water.
- these solvents are one or more hydrofluoroethers (HFEs) such as methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, isomeric mixtures of methyl nonafluorobutyl ether and methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl
- HFEs hydrofluoroethers
- HFE 7100 nonafluoroisobutyl ether
- HFE 7200 isomeric mixtures of ethyl nonafluorobutyl ether and ethyl nonafluoroisobutyl ether
- the fluorinated solvent may also be selected from a broad range of fluorinated solvents, such as chlorofluorocarbons (CFSs): C x Cl y F z , hydrochlorofluorocarbons (HCFCs): C x Cl y F z H w , hydrofluorocarbons (HFCs):
- CFSs chlorofluorocarbons
- HCFCs hydrochlorofluorocarbons
- HFCs hydrofluorocarbons
- C x F y H z purfluorocarbons (FCs); C x F y , hydrofluoroethers (HFEs): C x H y OC z F w , perfluoroethers: C x F y OC z F w , purfluoroamines: (C x F y ) 3 N, trifluoromethyl (CF3)- substituted aromatic solvents: (CF3)xPh [benzotrifluoride,
- the photoresist solution can typically include the photoresist material as described above in a fluorinated solvent, for example HFE 7500. Additionally, when the photoresist is a chemically amplified resist material, such as a
- this solution can additionally contain a photoacid generator.
- An appropriate photoacid generator is 2-[l - methoxy]propyl acetate (PGMEA).
- solvent in which the photoresist is dissolved have a higher boiling point than the first, second, or third fluorinated solvents.
- the fluorinated solvent applied to form the photoresist solution can have a boiling point above 110 degrees Celsius while the second and third fluorinated solvents can have a boiling point below 1 10 degrees Celsius.
- the solvent in the fluorinated solvent can include HFE 7500 having a boiling point of 131 degrees Celsius at atmospheric pressure while the first, second and third solvents can include HFE 7200 having a boiling point of 76 degrees Celsius at atmospheric pressure.
- any baking or drying step performed after the fluorinated photoresist is spun onto the substrate should be performed at a temperature less than the boiling point of the fluorinated solvent in which the fluorinated solvent is dissolved.
- the first, second and third fluorinated solvents can include a solubilizing agent to permit the pattern of exposed photo-patternable material to become soluble in the fluorinated solvent.
- a solubilizing agent to permit the pattern of exposed photo-patternable material to become soluble in the fluorinated solvent.
- materials such as a silazine, for example hexamethyldisilazane (HMDS; 1 , 1,1 ,3,3,3-hexamethyldisilazane) can be added to the first, second and third fluorinated solvents to render the patterns of exposed fluorinated photo-patternable layers soluble.
- Such an agent can be added to a fluorinated solvent to form the second and third solvents, for example the third solvent can contain 5% HMDS and 95% HFE 7200.
- Other useful solubilizing agents include isopropyl alcohol (IPA) which can be formulated similarly to form a third solvent containing 5% IPA and 95% HFE 7200.
- the first, second and third fluorinated solvents can have different reactivity levels with the first fluorinated solvent being weaker than the second or third fluorinated solvent and the second fluorinated solvent being weaker than the third fluorinated solvent.
- the first fluorinated solvent can be HFE 7300 (commercially available from 3M as Novec 7300)
- the second fluorinated solvent can be HFE 7600 (commercially available from 3M as Novec 7600)
- the third fluorinated solvent can be HFE 7200 (commercially available from 3M as Novec 7200).
- the first and second fluorinated solvents can contain 5% HDMS and the third fluorinated solvent can contain 5% Isopropyl Alcohol (IPA).
- a portion of the photoresist can be exposed to radiation to form patterns of exposed fluorinated photoresist material and a second pattern of unexposed photoresist material.
- an ultraviolet lamp having a wavelength of 248 nm can be used to radiate the photoresist or a lamp with another wavelength, for example 365 nm can be applied.
- an exposure of 84 mJ cm 2 at 248 nm is adequate to enable at least a first level of exposure the necessary reaction while a dose of 2700 mJ cm 2 is required when the wavelength is 365 nm. Higher levels of exposure can be applied to create additional exposure levels.
- non-fluorinated photo-patternable layer applies to any photo- patternable layer that does not contain highly fluorinated compounds. This is necessary to avoid a reaction between the materials used to form this layer and the "fluorinated photo-patternable layer" which is formed using the fluorinated photoresist materials as described earlier.
- This photo-patternable layer can be formed, for example, using any of the known standard photoresist materials as long as the chemistry does not interact with the fluorinated photo-patternable layer.
- These layers can include Shipley resists, such as NLOF 2020 (made by Dow) or SU- 8 (made by MicroChem).
- the resist can be strippable after patterning, in many embodiments liftoff can occur on the sacrificial fluorinated resist layer which can be deposited before the non-fluorinated photo-patternable layer.
- the formation of the non-fluorinated photo-patternable layer can include a post-apply baked (PAB) as well as a deposition step. It is important for this step that the PAB for the top resist layer not be applied at a greater temperature or with a longer duration than is applied during the formation of the fluorinated photo- patternable layer, since this may cause solvent from the fluorinated photo- patternable layer to form bubbles in the non-fluorinated photo-patternable layer.
- PAB post-apply baked
- non-fluorinated solvent applies to any non-fluorinated solvent which can be used to dissolve the non-fluorinated photo-patternable layer without interacting with the fluorinated photo-patternable layer.
- SU-8 chemistries gamma butyrolactone
- TMAH tetramethyl ammonium hydroxide
- forming or depositing either a fluorinated or non-fluorinated photo-patternable layer can include solution coating of a photoresist onto the substrate using methods such as spin coating and drying of this solution which can include a post-apply bake step.
- Exposing either of these photo-patternable layers can include selective exposure of the substrates to a radiation source such that different areas of the substrate receive at least three substantially different exposure levels and can further employ a post exposure bake to activate the chemical processes in the photo-patternable layers.
- the method in certain embodiments of the present invention is applied to form a generic device having at least two active layers that each receive a distinct pattern as a result of depositing photolithographic materials to form a single photo-patternable layer, exposing these materials to varying levels of radiation to create multiple patterns of material within the photo- patternable layer, depositing two or more active layers and developing different patterns to create different patterns within at least two of the active layers.
- Fig. 2 provides a flow diagram indicating the steps of this process.
- a substrate is provided 22.
- a layer of fluorinated photoresist is deposited onto the substrate and dried to form 24 a first fluorinated photo-patternable layer.
- This fluorinated photoresist can be a negative tone resist, such as Ortho 310 commercially available from Orthogonal Inc, but it could also be a positive tone resist.
- the substrate in this example can be either bare or with one or more patterned or unpattemed layers deposited before the photoresist.
- This fluorinated photoresist should have the property that it can receive varying amounts of UV light within its sensitivity range and, if chemically amplified, as is Ortho 310, varying amounts of post-exposure bake (PEB) temperature and time, to control the amount of solubility switching it receives in various parts of the deposited film. Once it is deposited, this first layer of fluorinated photoresist is baked to remove any residual solvents.
- PEB post-exposure bake
- An optional interlayer can then be deposited over the fluorinated photo- patternable layer to promote adhesion of following layers or to provide a photo- bleaching interlayer and dried to form 26 an optional interlayer.
- a second photoresist specifically a non-fluorinated photoresist is deposited on top of the fluorinated layer to form 28 a non-fluorinated photo-patternable layer.
- this non-fluorinated photo-patternable layer is assumed to also be a negative tone photoresist. However, this is not necessary and this non-fluorinated photo-patternable layer can have the same or a different tone than the fluorinated photo-patternable layer.
- This non-fluorinated photoresist layer is post-apply baked as well to remove any unwanted solvents. It is important for this step that the temperature applied for the post-apply bake for the non-fluorinated photoresist not exceed the temperature applied for the post-apply bake for the fluorinated photoresist layer, otherwise any additional solvent in the first photo-patternable layer can be vaporized and form bubbles in the non-fluorinated photoresist layer.
- the fluorinated and non-fluorinated photo-patternable layers form a photo- patternable bi-layer, which contains a single layer of fluorinated photoresist material.
- the photo-patternable bi-layer is then exposed 30 to UV light or radiation at a wavelength in which both resists are sensitive.
- the dose is varied across the substrate so that some regions or areas of the substrate receive a larger dose than other areas.
- it is preferable to expose both bi-layers with UV light having a single peak wavelength it is also possible to expose the substrate with radiation that has multiple peak wavelengths or to provide multiple exposures.
- the radiation or each exposure can have a different peak wavelength, one wavelength selected to expose the fluorinated photoresist and a second wavelength selected to expose the non-fluorinated photoresist.
- the photo-patternable bi-layer can be controlled to provide three to five or even more distinct exposure regions, each having a different pattern. The inventors have observed the ability to control this process to create:
- a first pattern including areas where neither the fluorinated or the non- fluorinated photo-patternable are exposed
- a third pattern including areas where the non-fluorinated photo-patternable layer is rendered insoluble to the standard developer and the fluorinated photo- patternable layer is insoluble to a first fluorinated solvent but soluble in a second fluorinated solvent as well as a fluorinated liftoff or third fluorinated solvent; a fourth pattern including areas where the non-fluorinated photo-patternable layer is rendered insoluble to the standard developer and the fluorinated photo- patternable layer is insoluble to the second fluorinated solvent but soluble in the fluorinated liftoff or third fluorinated solvent; and
- a fifth pattern including areas where the non-fluorinated photo-patternable layer is rendered insoluble to the standard developer and the fluorinated photo- patternable layer is soluble in the fluorinated liftoff or third fluorinated solvent.
- each of these patterns can be created and further, their removal can be controlled through exposure of these patterns to different solvents as indicated.
- This photobleaching interlayer can be the same or a similar photobleaching layer as is commonly used in high-resolution lithography as a resolution enhancement layer.
- the function of this layer is to absorb a certain amount of light before bleaching and permitting the ultraviolet radiation to pass through and encounter the fluorinated photo-resist layer.
- An additional benefit of such a layer can be to enhance the adhesion of the resist layer to the fluorinated layer.
- the first, the second, and the third or liftoff fluorinated solvents can all be highly fluorinated and can all be hydrofluoric ether (HFE) .
- the first fluorinated solvent can be Novec 7300
- the second fluorinated solvent can be Novec 7600
- the liftoff solvent can be Novec 7200+IPA. It is important that the second solvent be more reactive than the first solvent and that the liftoff solvent be more reactive than the second solvent, such that these solvents can be applied to remove the patterns with increasing exposure. Note that the standard developer is not a highly fluorinated solvent and therefore this solvent can have little or no effect on the material within the second, third, fourth, or fifth patterns.
- the substrate can be optionally baked 32 to cure the photo-patternable layers.
- This step is particularly important when the fluorinated photo-patternable layer or the non-fluorinated photo-patternable layer is a chemically amplified resist.
- This post exposure bake can often be performed at a temperature that is less than the temperatures used for either of the post apply bake steps discussed earlier.
- the non-fluorinated photoresist is then developed 34 to remove the non- fluorinated photoresist within the first pattern without removing the non-fluorinated photoresist in the second pattern.
- This develop 34 step is performed by exposing the substrate to a non-fluorinated solvent that serves as a solvent for the non-fluorinated photo-patternable layer.
- the substrate can be exposed to SU-8 chemistries such as gamma butyrolactone or tetramethyl ammonium hydroxide (TMAH).
- TMAH tetramethyl ammonium hydroxide
- the substrate can then be exposed 36 to a first fluorinated solvent to remove the unexposed fluorinated photo-patternable layer within the first and second patterns.
- This exposure can create an undercut under the non-fluorinated photo- patternable layer, which can be desirable for future liftoff steps.
- Each of these steps can be performed in a variety of environments, including open air or a near atmospheric pressure dry nitrogen environment. Note also, it is possible to divide this step 36 into two separate steps, including exposing the substrate to the first fluorinated solvent for a first time period to remove the unexposed fluorinated photo-patternable layer within the first pattern, and then exposing the substrate to the first fluorinated solvent for a second time period to remove the exposed fluorinated photo-patternable layer within the second pattern. Active material layers can be deposited between these steps to provide a patterned layer.
- a first active layer can then be deposited 38 over the substrate.
- This first active layer might be, for example, a conductive layer.
- This deposition process can be performed within an inert environment, including a vacuum or dry nitrogen environment.
- the substrate can then be exposed 40 to a second fluorinated solvent to remove the fluorinated photo-patternable layer within the third pattern.
- This step can liftoff the non-fluorinated photo-patternable layer within the third pattern as well as the portion of the first active layer that is deposited over the third pattern, thus this exposure creates a pattern within the first active layer.
- This exposure can be performed within a dry nitrogen environment in a near-atmospheric environment.
- a second active layer can then be deposited 42 over the substrate.
- This second active layer might be, for example, an organic semiconductor.
- This deposition process can also be performed within an inert environment.
- the substrate can then be exposed 44 to a third fluorinated solvent to remove the fluorinated photo-patternable layer within the fourth pattern.
- This step can liftoff the non-fluorinated photo-patternable layer within the fourth pattern as well as the portion of the second active layer that is deposited over the fourth pattern, thus this exposure creates a pattern within the second active layer that is different than the pattern created within the first active layer.
- This exposure can be performed within a dry nitrogen environment at near-atmospheric pressure.
- a third active layer can then be deposited 46 over the substrate.
- This third active layer might be, for example, a second conductor.
- This deposition process can also be performed within an inert environment.
- the substrate can then be exposed 48 to a liftoff solvent to remove the fluorinated photo-patternable layer within the fifth pattern.
- This step can liftoff the non-fluorinated photo-patternable layer within the fifth pattern as well as the portion of the third active layer that is deposited over the fifth pattern, thus this exposure creates a pattern within the third active layer.
- This exposure can be performed within a dry nitrogen environment at near- atmospheric pressure.
- these steps provide a method for forming an organic device by depositing a fluorinated photo- patternable layer over a substrate, forming a first and a second active layer over the substrate where at least one of the first or second active layers including an active organic layer and applying the photo-patternable layer to form a first pattern within the first active layer and a second, different pattern within the second active layer.
- these steps also provide a method for forming a device that includes depositing a fluorinated photo-patternable layer over a substrate; depositing a non- fluorinated photo-patternable layer over the substrate; exposing the fluorinated photo-patternable layer and the non-fluorinated photo-patternable layer to a radiation source providing three or more distinct levels of radiation, including at least a first pattern including areas where neither the fluorinated or the non- fluorinated photo- patternable are exposed, a second pattern including areas where one of the non- fluorinated photo-patternable layer and the fluorinated photo-patternable layer are exposed and the remaining layer remains substantially unexposed, and a third pattern including areas where both the non-fluorinated photo-patternable layer and the fluorinated photo-patternable are exposed; forming a first and a second active layer over the substrate; exposing the substrate to a non-fluorinated solvent to remove a portion of the non-fluorinated photo-pattern
- a substrate 70 is provided as shown in FIG. 3A.
- This substrate 70 can include active matrix driving circuits (not shown) for providing current to OLED devices. These circuits can be connected to power busses on the substrate (not shown) for providing current to the OLEDs that are connected to external power supplies and drivers for controlling the state of the circuits to control the flow of power from the power busses to the OLED.
- These circuits can be connected to conductive elements 72a, 72b, 74a, 74b on the surface of the substrate 70 where these conductive elements include an array of one or more electrodes 72a, 72b for sourcing or delivering current from an OLED within the first addressable light-emitting layer and an array of one or more via connectors 74a 74b for sourcing or delivering current to or from OLEDs in both the first and second addressable light-emitting layers.
- the entire substrate 70, with the exception of these conductive elements 72a, 72b, 72c, 72d will typically be covered with an insulating layer (not shown), which can serve as a pixel definition layer.
- edges between this insulating layer and the conductive elements 72a, 72b, 74a, 74b can have a vertical profile that includes a taper from the thickest part of the insulating layer to the conductive element 72a, 72b, 74a, 74b where the taper has a slope of 45 degrees or less and the insulating layer can overlap the edges of each conductive elements 72a, 72b, 74a, 74b.
- This structure is well known for short reduction in existing, single layer OLED structures.
- a photo-patternable layer 76 can then be formed over the substrate as shown in FIG. 3B and the conductive elements 72a, 72b, 74a, 74b.
- the formation of this photo-patternable layer can include the formation of a bi-layer of fluorinated and non-fluorinated photoresist materials as discussed earlier and shown in FIG. 2 in steps 24 through 28.
- the photo-patternable bi-layer is exposed 50 to radiation to create three unique patterns of material.
- the first pattern includes of the areas 78a and 78b as shown in FIG. 3C and is exposed such that neither the fluorinated nor the non- fluorinated photo-patternable are exposed within the areas 78a and 78b.
- the second pattern includes areas 80a and 80b. This pattern is exposed such that the non-fluorinated photo-patternable layer is rendered insoluble to the standard developer and the fluorinated photo-patternable layer is soluble in either a first fluorinated solvent or a second fluorinated solvent.
- the third pattern includes area 82 which is exposed such that the non-fluorinated photo- patternable layer is rendered insoluble to the standard developer and the fluorinated photo-patternable layer is insoluble in the first fluorinated solvent but soluble in the second fluorinated solvent within specified exposure conditions.
- the substrate is then exposed to the non-fluorinated developer to remove the non-fluorinated photo-patternable layer in the first pattern, including areas 78a and 78b.
- the substrate is then exposed to a fluorinated developer to remove the fluorinated photo-patternable layer in the first pattern, including areas 78a and 78b.
- both the fluorinated and non-fluorinated photo-patternable layers are removed from the substrate in the first pattern, including areas 78a and 78b as shown in FIG. 3D.
- these exposure steps can provide sidewalls in the remaining photo-patternable bi-layer that are undercut with a small portion of the fluorinated photo-patternable layer removed from under the remaining non- fluorinated photo-patternable layer.
- subsequent blanket coated layers can generally not be deposited in the areas shadowed by the top of this undercut profile.
- the substrate 70, the conductive elements 72a, 72b, 74a, 74b and any insulating layers, as well as the photo-patternable layers are generally not susceptible to contamination in uncontrolled atmospheric
- this step is to expose the one or more electrodes 72a and 72b, as well as the area around the one or more vias 74a, 74b.
- an organic light-emitting layer 84 is then deposited over the substrate 70 as shown in FIG. 3E.
- this active layer is formed such that electrical contact is made between the organic light-emitting layer and each of the one or more electrodes 72a, 72b, without forming electrical contact with the one or more vias 74a, 74b.
- a first light-emitting layer is formed in electrical contact with a first array of electrodes.
- the material forming the organic light-emitting layer in this example can be a small molecule organic light-emitting layer, which can be quite sensitive to the presence of oxygen or moisture.
- this step can be performed within a vacuum using vapor deposition.
- the organic light-emitting layer 84 is a small molecule layer it can include several sublayers, including a hole transport layer a light-emission layer and an electron transport layer.
- a very thin, typically less than 50 nm, metal or metal oxide layer can optionally be formed over the organic layer.
- a very thin layer of MgAg can be deposited. This layer can support electron injection but more importantly to this process, it can form a mechanical stabilizing layer to prevent mechanical damage to the small molecule organic light-emitting layer in subsequent steps.
- the organic light-emitting layer be formed of small molecule organic material and it can alternately be composed of a polymeric organic light-emitting material in which case it can be spun coat or otherwise solvent coated across the substrate and dried.
- a layer can be cross-linked, it can be mechanically stable and deposition of the very thin metal or metal oxide layer is not useful in providing mechanical stabilization as it can be when applying an active layer of small molecule organic materials.
- the substrate is then exposed to the first fiuorinated solvent.
- This step can be performed in a dry nitrogen environment at near atmospheric pressure.
- This step removes the second pattern of the fiuorinated photo-patternable layer, removing the fiuorinated photo-patternable layer within areas 80a and 80b.
- the layers coated over it, including the non-fluorinated photo-patternable layer and the organic light-emitting layer 84 is removed in the areas of this second pattern. Therefore the one or more via connectors 74a, 74b are exposed as shown in FIG. 3F.
- a conductive layer 88 for example a doped metal oxide layer such as ITO, 5 is then deposited over the substrate as shown in FIG. 3G.
- this conductive layer forms electrical contact with both of the one or more via connectors 74a, 74b and the top of the light-emitting layer.
- the conductive layer 88 can be capable of conducting current from the one or more vias 74a, 74b to the top of the first light-emitting layer and can serve as a second electrode.
- This step can be performed in a dry nitrogen environment at near atmospheric pressure. This step can also be conducted in a vacuum.
- the distance between the connectors and the electrode should be larger than the thickness of the organic light-emitting layer such that the resistance between the via connectors and the electrodes is minimized when the current passes through the diode that is formed between the conductive layer 88 and the electrodes 72a, 72b. This is useful to prevent current from flowing from the via connectors 74a, 74b and the electrodes 72a, 72b without passing through the diode and permitting light emission.
- the substrate is exposed to the second fluorinated solvent.
- this step can be performed in a dry nitrogen environment at near atmospheric pressure.
- This solvent removes the third pattern within the fluorinated photo-patternable layer and all layers that have been subsequently deposited on top of it.
- the organic material and the second electrode is removed between each effective light-emitting element, leaving only areas 90a and 90b as shown in FIG. 3H.
- This step completes the patterning.
- the first active layer namely the organic light-emitting layer has received a first pattern, that includes openings for the via connectors and the areas between subpixels corresponding to the second and third patterns.
- this organic device has been constructed by depositing a fluorinated photo- patternable layer over a substrate, forming a first and a second active layer over the substrate, at least one of the first or second active layers including an active organic layer, and applying the photo-patternable layer to form a first pattern within the first active layer and a second, different pattern within the second active layer.
- a bi-layer 92 including a second organic light- emitting layer and a final conductive layer, serving as a sheet electrode, are deposited over the substrate.
- This step can be performed in a dry nitrogen environment at near atmospheric pressure or, if vapor depositing organic small molecule materials can be performed in a vacuum coater.
- the voltage can be controlled independently to the portion of the first and second electrodes within each light-emitting element to independently control current to each layer of the OLED device.
- This method can provide a very high resolution OLED device with two colors of emission through a simple patterning process.
- one of the organic light-emitting layers can be deposited through a pair of shadowmasks to provide a full color device.
- color filters can be applied with the device to form a full color device.
- the OLED device is composed of several individually controlled pixels, permitting the OLED device to function as a display or lamp.
- this control is not necessary for all OLED devices and can therefore be simplified within some embodiments and especially for some OLED lamps which can provide control of the two layers to permit the color of light to be adjusted.
- each light-emitting layer can be composed of either small molecule or polymer organic materials.
- polymeric materials are typically applied at near atmospheric pressure while small molecule materials are typically applied in a vacuum, forming this first light-emitting layer from a polymer reduces the number of transitions between a vacuum and atmospheric pressure environment, which can be time consuming and costly.
- a green polymeric light-emitting material can be applied as the first light-emitting layer through spin, hopper or other solution coating means.
- the second light-emitting layer can be formed from small molecule materials.
- this layer can include a magenta light-emitting layer or include both red and blue light-emitting materials that is formed from small molecule light-emitting materials. This can be important as the small molecule red and blue light-emitting materials are typically more efficient than comparable polymeric materials and further the lifetime of the blue small molecule organic light-emitting materials is typically significantly longer than the lifetime of the blue polymer organic light-emitting materials.
- an array of one or more inorganic thin film transistors are formed using an etching, rather than a liftoff, process to provide the desirable electrical component.
- the steps used to form a particular device containing an array of one or more bottom gate TFTs are depicted in the process diagram of FIG. 4 and listed in the flow diagram of FIG. 5. While it should be noted that the particular device depicted and discussed here includes an array of bottom gate, inorganic TFTs, one skilled in the art will recognize that this the current invention is not limited to this particular embodiment and other devices, including top gate, organic TFTs or other patterned solid state electronics elements could be formed using the methods of the present invention.
- a substrate 150 is provided 200 as shown in FIG. 5.
- the active layers useful in forming the TFTs within the device are then blanket coated 202 across the substrate as shown in FIG. 4B. These layers can include a first conductive metal layer 152 deposited near the substrate, a dielectric layer 154 deposited over the first conductive metal layer, a semiconducting layer 156
- the first conductive metal layer can be formed from a different material from the second conductive metal layer.
- the first conductive metal layer 152 can be formed of chrome and the second conductive metal layer 158 can be formed of aluminum.
- FIG. 4C shows these active layers 152, 154, 156, 158 as a single layer 160.
- a 5 fluorinated photo-patternable layer 162 is formed 204 over the active layers 160.
- a non-fluorinated photo-patternable layer 164 is formed 206 over the fluorinated photo-patternable layer.
- the fluorinated and non- fluorinated photo-patternable bi-layer provide a photo-patternable bi-layer.
- this photo-patternable bi-layer has been created and dried as described earlier, it is exposed 208 to multiple levels of radiation, in this example the photo-patternable bi- layer is exposed to four different levels of radiation, to create four different patterns within the photo-patternable bi-layer.
- the first pattern includes the areas outside the effective TFT structure, including area 166a as depicted in FIG. 4E.
- this first pattern 166 also includes areas 166b and 166c as shown in FIG. 4E. These areas provide access to the first metal conductive layer for later etching steps. Four similar areas are indicated in FIG 3E for each of the two TFTs that will be illustrated.
- the second pattern 168 is exposed, such that the non- fluorinated photo-patternable layer 166 is exposed to radiation while the underlying fluorinated photo-patternable layer 162 is not exposed to radiation. In FIG. 4E, this pattern is indicated by areas 168a, 168b, 168c, 168d.
- the semiconductor and dielectric can also be optionally removed in these areas.
- the third pattern includes areas 170a, and 170b, which can provide the channels for the bottom gate TFTs of the current arrangement.
- This third pattern 170 can be exposed such that both the non-fluorinated photo-patternable layer 164 and the fluorinated photo-patternable layer can be exposed. However, the fluorinated photo-patternable layer can be exposed to a first amount of radiation.
- the remaining areas, including 172a, 172b, and 172c are included within a fourth pattern 172.
- This pattern is exposed such that both the non-fluorinated photo-patternable layer 164 and the fluorinated photo-patternable layer can be exposed.
- the fluorinated photo-patternable layer can be exposed to a second amount of radiation which is higher than the first amount of radiation.
- the substrate is then exposed 210 to a non-fluorinated solvent, which removes the non-fluorinated photo-patternable layer 164 from the areas of the first pattern 166.
- a non-fluorinated solvent which removes the non-fluorinated photo-patternable layer 164 from the areas of the first pattern 166.
- This provides the structure illustrated in FIG. 4F with the non- fluorinated photo-patternable layer removed in the areas of the first pattern, exposing the fluorinated photo-patternable layer 162 outside the regions of the non- fluorinated photo-patternable layer 164.
- the Substrate 150 is then exposed 212 to a first fluorinated solvent for a first set of exposure conditions, including a first set of time, agitation and temperature conditions. This exposure, removes the fluorinated photoresist within the areas defined by the first pattern 166.
- both the fluorescent and non-fluorescent photo-patternable layers are removed within the first pattern, exposing the active layers 160. Both the fluorescent and the non-fluorescent photo- patternable layers remain in the areas defined by the second 168, third 170 and fourth 172 patterns.
- the substrate is then etched 214 using any process capable of removing the active layers to remove the exposed materials within the second conductive metal layer 158, the semiconductor layer 156, and the dielectric layer 154.
- the etching process can be an ion etching process and include either physical ion etching, also called dry etching, or assisted physical ion etching, referred to as wet etching.
- these particular etching processes are not required and one skilled in the art will recognize that a variety of different etch processes could be utilized without departing from the scope and spirit of the present invention.
- This etching is completed in such a way that at least the second conductive metal layer 158, the semiconductor layer 156, and the dielectric layer 154 are removed within the areas of the first pattern 166, using for example, a series of dry etch steps to remove each layer.
- a second etch step preferably a wet etch step can be used to remove the first conductive metal layer 152. This step, not only removes the first conductive metal layer 152 in the areas within the first pattern 166 to expose the bare substrate in these areas, but it permits a significant undercut to be obtained, removing at least a portion of this first conductive metal layer outside the first pattern.
- first pattern included areas 166b and 166c which are internal to a portion of the second conductive metal layer that is desired. These areas permit features, including 174a, 174b to be formed through the desired second conductive metal layer, the semiconducting layer and the dielectric layer by applying the solvents and the dry etching steps.
- These features 174a, 174b then permit the first conductive metal layer to exposed to the wet etching step such that the undercut created by this wet etching step can remove the first conductive metal layer within the regions of these features 174a, 174b, eliminating a portion of the first conductive metal layer near the TFT such as in the area 176 indicated in FIG. 4H. This permits the gate of the TFT to be isolated from the remaining portions of the first conductive metal layer to prevent shorting of this component.
- the photo-patternable bi-layer can protect the portion of each of the active layers within the second, third and fourth patterns from being removed by the etching process other than very thin features within the first conductive metal layer.
- This wet etching process can use chemicals that are selective to the material applied in the first conductive metal layer such that only this layer is affected by this process.
- a similar use of dry and wet etching have been described earlier by Taussig et al. in US Patent 7,202,179, issued on April 10, 2007 and entitled "Method of forming at least one thin film device”.
- the substrate can then be exposed 216 once again to the first fluorinated solvent for a second set of exposure conditions, including a first set of time, agitation and temperature conditions.
- This second set of exposure conditions can have a time longer than the duration of the first set of exposure conditions.
- This exposure can permit the first fluorinated photo-patternable layer 162 to lift off, removing the overlying non-fluorinated photo-patternable layer 164 and exposing the second conductive metal layer 158 in the areas within the second pattern.
- the substrate undergoes an etch 218, for example another dry etch, to remove at a least a portion of the active layers within the areas of the second pattern as shown in FIG. 4J. As shown in FIG.
- the second conductive metal layer 158, the dielectric layer 156 and the semiconductor layer 154 can be removed leaving only the first conductive metal layer 152 within the areas of the second pattern, however, in some arrangements at least a portion of at least the dielectric layer 154 can be left over the first conductive metal layer at the completion of this etching step.
- the substrate can then be exposed 220 to a second fluorinated solvent for a set of exposure conditions.
- This second solvent can permit the first fluorinated photo-patternable layer 162 to lift off, removing the overlying non-fluorinated photo-pattemable layer 164 and exposing the second conductive metal layer 158 in the areas 170a, 170b of the third pattern as shown in FIG. 4K.
- a dry etch is applied 222, which removes the second conductive metal layer 158 within the areas 170a, 170b.
- the substrate can then optionally be exposed 224 to a third fluorinated solvent for a set of exposure conditions.
- This third fluorinated solvent strips the remaining fluorinated photo-patternable layer 162, removing the remaining portions of the non-fluorinated photo-patternable layer 164.
- the final structure is shown in FIG. 4L.
- This structure includes a substrate 150. Over this substrate at least the first conductive metal layer 152 and the second conductive metal layer 158 are patterned differently as a result of applying a single photolithographic step that included depositing the photo-patternable bi-layer and a single exposure step which exposed the photo-patternable bi-layer to three or more, in this example four, different levels of exposure to create four separate patterns within the photo- patternable bi-layer.
- the first conductive metal layer is patterned to provide only two connections to the gate, removing material in other areas, including area 176. Over this the dielectric layer 154 and semiconductor layer 156 are patterned, in this case these two active layers receive the same pattern, however, the pattern imparted to the dielectric layer 154 and the semiconductor layer 156 is different than the patterns imparted to either the first conductive metal layer 152 or the second conductive metal layer.
- the pattern imparted to the first conductive metal layer 152 permits it to function to provide the gate and the data lines for an array of TFTs on a substrate.
- the pattern imparted to the dielectric layer permits it to prevent the flow of current from the first conductive metal layer 152 to the semiconductor layer 156.
- the semiconductor layer bridges the source and drain that are created in the second conductive metal layer through the formation of areas 158, which serves as the channels for the TFTs in the array.
- a method for forming a device, specifically an array of TFTs, wherein this method included providing a substrate; depositing a fluorinated photo-patternable layer over the substrate; forming a first and a second active layer over the substrate; and applying the photo-patternable layer to form a first pattern within the first active layer and a second, different 6565 pattern within the second active layer.
- This method permitted the formation of different patterns in the different active layers by depositing a non-fluorinated photo- patternable layer over the substrate to form a functional photo-patternable bi-layer with the fluorinated photo-patternable layer and exposing the photo-patternable bi- layer to a radiation source providing three or more distinct levels of radiation to create three or more patterns within the photo-patternable bi-layer.
- a first non-fluorinated solvent was applied to remove a pattern of the non-fluorinated material within the non-fluorinated photo-patternable layer and at least two separate fluorinated solvents are applied to independently remove the fluorinated material within the different patterns of the fluorinated photo-patternable layer.
- the first and second active layers were deposited on the substrate before the photo- patternable bi-layer and the step of applying the photo-patternable layer to form a first pattern within the first active layer and a second, different pattern within the second active layer included exposing the substrate to one or more solvents to remove the photo-patternable bi-layer within the first pattern within the photo- patternable bi-layer; exposing the substrate to a first etching process to remove at least a first portion of the first active layer within a first of the three or more patterns within the photo-patternable layer; exposing the substrate to one or more solvents to remove the photo-patternable bi-layer within a second pattern; and exposing the substrate to a second etching process to remove at least a second portion of the second active layer within a second of the three or more patterns within the photo- patternable layer.
- the method included exposing the substrate to one or more additional solvents to remove the photo-patternable bi-layer within at least a third of the three or more patterns within the photo-patternable layer and patterning a first, second, and third active layer differently where these active layers included two conductive layers and a semi-conductor.
- the preceding method for forming a thin-film transistor therefore included providing a substrate; coating. active layers, including a first conductive layer, a dielectric layer, a semiconducting layer, and a second conductive layer, over the substrate; forming a photo-patternable layer including a fluorinated photo- patternable layer over the active layers; exposing the photo-patternable layer to a radiation source providing three or more different levels of radiation to different patterns within the photo-patternable layer; and exposing the photo-patternable layer 2012/026565 to solvents to selectively remove the different patterns, applying one or more etching steps between the removal of the different patterns to provide the structural components of the TFT.
- certain aspects of the present invention provides a method for forming a device, including: providing a substrate; depositing a fluorinated photo- patternable layer over the substrate; forming a first and a second active layer over the substrate; and applying the photo-patternable layer to form a first pattern within the first active layer and a second, different pattern within the second active layer.
- Various embodiments of this method have been described herein.
- certain aspects of the invention enables the efficient creation of certain OLED display architectures that have not been realized through efficient processes within the prior art.
- certain aspects of the invention provides a method for employing a single photo-lithographic step to form a structure including at thin film transistor on a substrate.
- bi- layers of fluorinated and non-fluorinated photo-patternable layers can be formed and exposed to radiation and solvents to selectively remove the photo-patternable layer within three or more different areas within the photo-patternable layer.
- fluorinated photo-patternable layers can be employed and exposed to at least three different levels of radiation to create three different patterns and different solvents or exposure conditions to selectively remove material from these three different patterns.
- the examples have illustrated that methods can be developed from these two observations, either singly or in combination to provide a method in which three or more patterns are created within a single photolithographic step to efficiently form high performance devices.
- the photo- patternable layer can be deposited before one or more of the active layers and the patterns can be imparted to the active layer through liftoff.
- the photo-patternable layer can be deposited after one or more of the active layers and the patterns can be imparted to the active layer through etching.
- the step of exposing the photo-patternable layers to radiation can take place in environments containing oxygen or water. As these environmental factors can have a negative effect on the performance of certain organic and inorganic material layers, it is sometimes desirable that the photo-patternable layers be deposited and exposed prior to deposition of certain organic or highly reactive inorganic materials, including layers containing magnesium, lithium, and organic semiconductors, especially small molecule organic semiconductors.
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KR1020137023075A KR20140019341A (en) | 2011-03-03 | 2012-02-24 | Process for patterning materials in thin-film devices |
EP12752927.9A EP2681781A4 (en) | 2011-03-03 | 2012-02-24 | Process for patterning materials in thin-film devices |
US13/985,194 US20150364685A1 (en) | 2011-03-03 | 2012-02-24 | Process for patterning materials in thin-film devices |
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US10580987B2 (en) | 2014-08-01 | 2020-03-03 | Orthogonal, Inc. | Photolithographic patterning of organic electronic devices |
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WO2016105473A1 (en) | 2014-12-24 | 2016-06-30 | Orthogonal, Inc. | Photolithographic patterning of electronic devices |
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- 2012-02-24 JP JP2013556751A patent/JP2014515178A/en active Pending
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DE102014117096A1 (en) * | 2014-04-01 | 2015-10-01 | Technische Universität Dresden | Photolithography method for producing organic light-emitting diodes |
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US10580987B2 (en) | 2014-08-01 | 2020-03-03 | Orthogonal, Inc. | Photolithographic patterning of organic electronic devices |
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Also Published As
Publication number | Publication date |
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US20150364685A1 (en) | 2015-12-17 |
JP2014515178A (en) | 2014-06-26 |
CN103348503A (en) | 2013-10-09 |
WO2012118713A3 (en) | 2012-11-29 |
KR20140019341A (en) | 2014-02-14 |
EP2681781A2 (en) | 2014-01-08 |
EP2681781A4 (en) | 2014-09-03 |
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